CA1214100A - Fungicide compound - Google Patents

Abstract

ABSTRACT

N-(2-METHYL-5-CHLOROPHENYL)-N-METHOXYACETYL-3-AMINO-1,3-OXAZOLYDIN-2-ONE AND FUNGICIDE
COMPOSITIONS CONTAINING SAME

N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3-amino-1,3-oxazolydin-2-one exhibits decidedly superior fungicidal activity than other compounds of its class. The compound has both preventative and curative action and may be applied in conventional formulations

Description

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N-(2-METHYL-5-CHLOROPHENYL)-N-METHOXYACETYL-3-AMINO-1,3-OXAZOLYDIN-2-ONE AND FUNGICIDE
COMPOSITION CONTAINING SAME

This invention relates to a compound endowed with Eungicidal activity and in particular to the compound N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3-amino-1,3-oxazolydin-2~one and to its use in combatting fungal infections in useful plants and to fungicide compositions containing same.
Belgian Patent Specification No. 885,117 discloses fungicide compounds belonging to the class of N-aryl-N-acyl-3-amino-1,3-oxazolydin-2-ones including compounds within the general formula:
/o\

\ N

R1 ~ 1 - C - C32 - OC~l3 in which:
R, Rl and R2 independently represent a hydrogen atom, a halogen atom or an alkyl or alkoxy group either of which contains 1 to 4 carbon atoms.

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Subsequent research on such compounds has revealed that the position of substituents R, R1 and R2 on the aromatic ring, is of particular importance.
In particular, the compounds of formula (I) in which at least one of the ortho positions is unsubstituted are endowed with good fungicidal activity and the particular compound N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3 amino-1,3-oxazolydin-2-one is surpr.isingly endowed with a definitely superior fungicidal activity.
Therefore according to the present-invention there is provided the compound N-(2-methyl-5-chloro phenyl)-N-methoxyacetyl-3-amino-1,3 oxazolydin 2-one of the formula: , C~ N/ (II) CH

N ~ _ CH2 - OCH3 ~.
Compound (II) is endowed with a particularly high fungicide activity and may be used, either alone or in the form of a suitable composition, to combat fungal infection in plants of agricultural importance.

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In accordance with the present invention there i5 thus provided a fungicide composition comprisiny, as active ingredient, the compound (II~ as defined above together with a li~uid or solid inert carrier. The composition may additionally comprise zinc and magnesium ethylene-bis-dithiocarbonate.

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Also according to the invention there is provided a method of protecting agricultural cultivations against the attack of phytopathogenous fungi comprisiny administering an effective amount of compound (II) and fungicidal compositions containing compound (II) as aetive ingredient.
The preparation of compound (II) may be conducted according to the general reaetions disclosed in Belgian Patent Specifieation No. 885,117. By following a proeess analogous to that described in said Patent and starting from 2-methyl-5~ehloro-phenyl-hydrazine, compound (II) was obtained with good yields in the form of a thick oil exhibiting a refraetive index at 50C of 1,5375.
After crystallisation from ethyl acetate plus ligroin, compound (II) was obtained in the form of a white erystalline solid having a melting point of 69 to 70C.
IR analysis (main absorption bands):
2930, 1775, 1710, 1490, 1410, 1130 and 1035 em 1.
Compound (II ? is endowed with a high fungicidal activity which is particularly effeetive against fungi belonging to the elass of Phyeornicetes.
As will be illustrated in the Examples herein-after the f-lngieidal aetivity of eompound ~II) is definitely superior to that of other compounds of formula (I) in whieh at least one of the ortho =4=
positions of the aromatic ring is unsubstituted.
Compound (I~) is perfectly compatible with the plants to be protected from the phytopathogenous funyi attack and exhibits a phyto-toxicity inferior to that of many compounds described in the above refererlced Belgian ~atent~ Cornpound (II) develops both a curative as well as a preventative action and is endowed with remarkable systemic properties.
These characteristics allow compound (II) to be used both for preventing attacks to the useful cultivations and curing diseases caused therein by phytopathogenous fungi belonging particularly to the following genera: Peronospora, Phytophtora, Plasmopara, Pseudoperonospora and Pythium.
The high activity of compound (II) makes it possible to uti]ise very low effective dosage rates which, depending on different factors, e~g. the type of cultivation to be protected, the type and the degree of fungal infection foreseen or present~
climatic (weather) factors and environmental conditions, may range from 1 to 100 g/ha.
For practical purposes it is useful to apply compound (II) in the form of suitable compositions which can be dilutd with water before use.
Compositions containing, as active ingredient, compound (II) may be prepared in the form of a liquid .. . .

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concentrate, emulsifiable concentrate, dry power or wettable powder in accordance with conventional formulative practice. Such compositions may comprise, in addition to compound (II), inert liquid or solid carriers and optionally one or more other additives, e.g. emulsifiers, surfactants, wetting agents and suspending agents.
If desired, it is possible to include in the fungicide compositions other active substances effective in the agricultural field and compatible with compound (II), e.g. herbicides, fertilizers, biostimulants and other fungicides.
In particular, it has been found that for certain types of applications the co-formulation of compound (II) together with other, so-called ~coverage", fungicides is very effective. These fungicides may belong to one of the following classes: alkylene-bis-dithiocarbamates, copper salts or oxides and N-haloalkylthio-imides. Examples of such fungicides are compounds known by the following common names: Zineb, Maneb, Mancozeb, Nabam, copper oxychloride, Captan, Captafol and Folpet.
The invention will now be illustrated by the following Examples.

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Exalnple 1 C~lrative activity against P asmo~)ara vlticol~ on vine p]ants.
~eneral methodolo~
__ The leaves of cv. Dolcetto vine plants, grown in pots, in a conditioned environment at 25C and at 60% relative humidity, were besprinkled on their lower surface with an aqueous suspension of condidia of Plasmopara viticola (~. et C.) Berl et de Toni (200,000 conidia/cc). After a residence time of 24 hours, in a humidity saturated environment at 21C, the plants were divided into three groups. The plants of each group were then treated, by besprinkling both leaf surfaces, with the product under examination, dissolved in a water/acetone solution (acetone = 20%
by volume), respectively after l, 2 and 3 days from the infection date.
At the completion of the incubation period (7 days), the degree of infection was evaluated according to an evaluation scale ranging from lO0 (for a healthy plant) to 0 (for a completely infected plant).
The following Table 1 reports the data for the curative activity against P.viticola of compound (II) by comparison with the data of seven other compounds (A, B, C, D, E, F and G) of formula (I).

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From the data in Table 1 it will readily be appreciated that compound (II) possesses a funyicidal activity that is definitely superior to that of the comparative compounds. Furthermore, the funcidical activity of compound (II) is particularly high in an absolute sense since this compound still displays a full activity (with a 100% reduction of the rungal infection) at extremely low doses (0.0005%).

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Example 2 Curative action ayainst Peronospor tabacina on tobacco p:lants.
_neral methodology Leaves of tobacco plants of cv. Burley, grown in pots in a conditioned environment, were besprinkled on the lower leaf surface with an aqueous suspension of conidia of Peronospora tabacina Adam (200,00~
conidia/ml). After a residence time of 6 hours in a humidity saturated environment, the tobacco plants were divided into two groups and placed in an environment conditioned at 20C and 70% relative humidity, for the incubation of the fungusO ~fter 24 and 48 hours respectively from the moment of the infection the treatment of the first and the second group were treated by besprinkling both leaf surEaces with the product under examination in a water/acetone solution (acetone = 2~ by volume~. At the end of the incubation period (~ days) the degree of infection was evaluated according to an evaluation scale ranging from 100 (for a healthy plant) to 0 (for a completely infected plant).
The following Table 2 reports the data for the curative activity against P. tabacina of compound (II) in comparison with seven other compounds of formula (I) (A to G).

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From the data in Table 2 it will be readily appreciated that compound (II) possesses a ~ungici(3e activity which is decidedly superior to that of the comparative compounds and that the fungicidal activity of compound (II~ is extremely high in an absolute sense, in as much as a complete activity (100%
reduction of the fungal infection) at very low doses (0.0005%).

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_xample 3 Preventive action against Plas~ ra viticola on vine.
General methodology The vine leaves of cv. Dolcetto, grown in po~s in a conditioned environment, were besprinkled on the upper leaf surface with the product under examination dlssolved in a water/acetone solution at 20% of acetone (vol.!vol.).
The plants were then placed in a conditioned environment. Two series of plants were separately besprinkled on their lower leaf surfaces, 1 and 7 days from the day of treatment respectively, with an aqueous suspension of Plasmopara viticola conidia (200,000 conidia/cc) and, after 24 hours residence time in humidity saturated environment, were placed back in a conditioned environment.
~ t the end of the incubation period (7 days) the degree of infection was assessed. Compound (II) displayed a preventive action superior to that of the comparative compounds used in Example 1. Furthermore, the preventive activity against Plasmopara viticola of compound (II) proved to be extremely high in an absolute sense in as much as at very low doses (0.0005%) compound (II) was able to completely inhibit fungal infection both when the artificial infection was conducted 1 day and 7 days following teatment with compound (II).

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Example 4 Preventive activity against Peron~ora tabacina on tobacco.
Ger ral methodol~
cv. Burley tobacco plants grown in pots ina condit:ioned environment, were treated by besprinkling both leaf surfaces with the product under examination in a water/acetone solution at ~0% acetone (vol./vol.~. rrwO series of plants were treated respectively after 1 and 7 days, by besprinkling the lower leaf surface with an aqueous suspension of Peronosporo tabacina Adam conidia (200,000 -conidia/cc). After 6 hours dwell time in a humidity saturated environment, the treated plants were placed in an environment conditioned at 20C and 70% relative humidity for the incubation of the fungus.
At the end of the incubation period (6 days), the degree of infection was assessed. Compound (II) exhibited a fungicide activity decidedly superior to that of the comparative compounds used in Example 1.
Furthermore, the preventive activity against Peronos~o___tabacina of compound (II) is extremely high in an absolute sense in as much as, even when used in very low doses (i.e. 0.0005%), the compound is able to completely inhibit fungal infection both when the artificial infection is conducted 1 day and 7 days following the treatment with compound (II).

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The following Examples relate to fungicidal compositions containing as active ingredient compound ~II) alone or compound (II) in associaton with Mancozeb (zinc and manganese ethylene-bis-dithiocarbamate).
In these Examples the following abbreviations will be used:
DMF = N,N-dimethyl-formamide.
Xylene = commercially available mixture of xylene isomers.
Ca-DBS = calcium dodecylbenzenesulphonate, e.g. the product marketed by ROL-Montedison under the trade mark n Emulson AG/CaL n, COH-ETO = polyoxyethylated hydrogenated castor oil, e.g. the product marketed by ROL-Montedison under the trade mark QEmulson COH~.
SO-ETO = polyoxyethylated sorbitan-oleate, e~g. the product marketed by ROL-Montedison under the trade mark ~Emulson 20-OM n, NF-ETO = polyoxye~hylated nonylphenol, e.g.
the product marketed by ROL~Montedison under the trade mark Emulson 10B~.
Na-DSS = s~dium dialkylsulphosuccinate, e.g.
the product marketed by ROL-Montedison under the trade mark ~Madeol V40 a .

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Na-l.S = sodium lignosulphonate, e.g. the product marketed ~y Borregard under the trade mark ~ltrazina NA' and the product marketed by Cartiere di Tolmezæo under the trade mark "Bretaxn.
Na NS = sodium alkylnaphthalensulphonate, e.g.
the products marketed by ROL-Montedison under the trademarks ~Madeol W90~ and "Madeol 934~.
Example S
Compositions in emulsifiable concentrate (EC
Ingredients (by weight~:
A) Compound (II) 5 to 40%
B) Solvent 40 to 9~%
C) Surfactant 5 to 20 Suitable solvents (B~ are aromatic and alkyl-aromatic hydrocarbons, ketones, esters, DMF and mixtures thereof.
Suitable surfactants (C) are polyoxyethylated nonylphenol, polyoxyethylated triglycerides, polyoxyethylated fatty acids, sodium, calcium or triethanolammonium dodecylbenzensulphonate and mixtures thereof.
The preparation of the compositions is effected by dissolving compound (II) in the solvent and then admixing the surfactant. Examples of compositions in emulsifiable concentrate are reported in the followîng Table 3.

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Table 3 Compositions in emulsiEiable concentrate (ingredients in percent by w~ight) , _ _ ~
Compositions .
Ingredients1 3 r4 - 5 A) Compound (II) 20 5 15 30 40 B) Xylene 63 90 70 40 40 B~ Cyclohexanone 7 _ _ 10 B) DMF _ _ 3 _ 10 C) Ca-DBS 3 12.5 4 3 C) COH-ETO 3.5 _ 6 C)-SO-ETO _ 4 4.5 _ 3 C) NF ETO 3.5 _ 5 10 4 Example 6 Compositions in wettable powder -(WP) Ingredients (by weight):
A) Compound (II)5 to 50%
B) Wetting Agent0.5 to 5%
C) Suspending Agent1 to 5%
D) Carrier 40 to 93.5%

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Suitable wetting agents (B) are polyoxyethylated nonylphenol, sodium alkylnaphthalen-sulphonate, sodium dialkylsulphosuccinate and rnixtures thereof.
Suitable suspending agents (C) are sodium, calcium or aluminum lignosulphonate, sodium alkylnaphthalenesulphonate condensed with formaldehyde, maleic anhydride diisobutylene copolymers and mixtures thereof.
Suitable carriers (D) are fossil meal (diatomaceous earth) t kaolin, CaC03, SiO2 and mixtures thereof.
The preparation of the compositions in wettabie powder is carried out by grinding in a suitable mill the mixture of the ingredients to the established particle size.
The following Table 4 reports examples of compositions in wettable powder.

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rrable 4 Compositions in wettable powder (ingredien~s in percent by weight~.
_ Compositions Ingredients -: l 2 3 5 - 6 _ A) Compound (II) - 25 5 15 30 40 50 B) Na-DSS 2 _ _ 1 2 _ B) Na-NS _ 1 4 _ 2 _ B) NF-ETO _ _ _ _ 5 C) Na-LS 3 2 1 3 2 5 D3 Kaolin 70 92 60 61 _ 10 D) Fossil meal _ 20 _ 44 _ D) SiO2 _ _ 5 10 30 ~2~
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Example 7 Compositions in wettable powder of Compound (II) in association with Mancozeb _ Ingredients (by weight)-A) Compound (II)3 to 3%
~) Mancozeb 65%
C) Wetting Agent0.5 to 5~
D) Suspending Agent1 to 5%
E) Carrier 17 to 30.5%
Suitable wetting agents (C), suspending agents ~D) and carriers (E) are listed in Example 6.
The compositions may be prepared according to the technique described in Example 6.
Table 5 reports examples of composition in wettable powder.

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Tahle 5 Compositions in wettable powder of Compound (II) in association with Mancozeb (ingredients in percent by weight).

_ _ Compositions Ingredients 1 2 r 4 _ _ .
A) Compound (II) 6 3 4 8 B) Mancozeb 65 6565 65 C~ Na-DSS . 2 ~5 0.5 C) Na-NS 2.5 1 1 C) NF-ETO _ _ _ 0.5 D) Na-LS 5 3 2 3 E) Kaolin 18 26.5 _ 16 E) Fossil meal_ _ 23 E) SiO2 4 _ _ _ 6 =21=

E~ _8 Compositions in concentrated suspension of Compound (II) in ,association with Mancozeb _ _ _ Ingredients (by weight):
A~ Compound ~ 1.5 to 4%
B) Mancozeb 32.5 C) Surfactant .5 to 20~
D) Solvent 43.5 to 61%.
Suitable surfactants and solvents are listed in Example 5.
The compositions are prepared by dissolving compound (II) in the solvent and by admixing the ~urfactant. To the resulting mixture, Mancozeb is suspended under stirring until a homogenous mixture is obtained.
The following Table 6 reports examples of compositions in concentrated suspension of compound ~II) in association with Mancozeb.

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Table 6 Compositions in concentrated suspension (inyredients in percent by weight).

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Compositions Ingredients 1 2 ~

__ A) Compound (II) 3 1.5 2 4 B) Mancozeb 32.5 32.5 32.5 32.5 C) Ca-DBS 3 1 2 3 C ) COH-ETO 3.5 _ _ 2 C ) SO ETO _ 3 10 _ D ) NF-ETO 3.5 1 _ 1 D) Xylene 54~5 61 53.5 47.5 D) CYclohexanone _ _ _ 10 The compositions of Examples 5 to 7 have been texted for fungicidal activity against Plasmopara viticola on vines in open-field conditions. All the -compositions have shown excellent fungicidal activity in accordance with the high activity shown by compound (II) in laboratory experiments.

Claims (3)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. N-(2-methyl-5-chlorophenyl)-N-methoxyacetyl-3-amino-1,3-oxazolydin-2-one.

2. A method of combatting fungal infections on useful plants, comprising applying to said plants before or after the onset of infection, an effective amount of the compound as claimed in claim 1.

3. A method as claimed in claim 2, in Which the compound is applied to a cultivated area in an amount of from 1 to 100 g/ha.